WO2018176298A1 - Formaldehyde-free curable composition - Google Patents
Formaldehyde-free curable composition Download PDFInfo
- Publication number
- WO2018176298A1 WO2018176298A1 PCT/CN2017/078707 CN2017078707W WO2018176298A1 WO 2018176298 A1 WO2018176298 A1 WO 2018176298A1 CN 2017078707 W CN2017078707 W CN 2017078707W WO 2018176298 A1 WO2018176298 A1 WO 2018176298A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- curable composition
- acid
- dry weight
- polyolefin
- starting material
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the concentration of unreacted polycarboxylic compound in the reaction In addition to monitoring the amount of polycarboxylic compound added to the reaction, it is important to monitor the concentration of unreacted polycarboxylic compound in the reaction. That is, in concentration, the polycarboxylic compound, e.g. maleic anhydride, tends to undergo undesirable homopolymerization polymerization.
- the polymerization product is highly objectionable since it has a dark color, and tends to become dispersed in the functionalized polyolefin.
- 950P is polyolefin emulsion with SC of 39%, made from A-C TM 950P, a maleic anhydride modified polypropylene from Honeywell, with acid value of 33mg KOH/g;
- Comparative Curable Composition Example 2 used overdose polyolefin, and its wet strength is not acceptable.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paper (AREA)
Abstract
Description
Wet strength (kgf/inch) | |
Illustrative Example 1 | 3.59 |
Illustrative Example 2 | 4.24 |
Illustrative Example 2 at 50℃ for 15 days | 4.17 |
Illustrative Example 3 | 3.26 |
Illustrative Example 4 | 3.83 |
Illustrative Example 5 | 4.71 |
Illustrative Example 6 | 4.82 |
Illustrative Example 7 | 4.53 |
Comparative Example 1 | 3.01 |
Comparative Example 2 | 2.85 |
Comparative Example 3 | 2.8 |
Comparative Example 4 | 2.65 |
Claims (12)
- A curable composition comprising from 70 to 99%by dry weight based on total dry weight of the curable composition, an acrylic emulsion component, and from 1 to 30%by dry weight based on the total dry weight of the curable composition, a polyolefin emulsion component prepared by emulsifying a polycarboxylic-compound functionalized polyolefin starting material.
- The curable composition according to Claim 1 wherein the acrylic emulsion component comprises from 0.25 to 10%by weight based on the total weight of the acrylic monomers, copolymerized ethylenically unsaturated carboxylic acid monomer.
- The curable composition according to Claim 2 wherein the copolymerized ethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, and maleic anhydride.
- The curable composition according to Claim 1 wherein the polyolefin starting material is selected from the group consisting of thermally degraded homopolymers and copolymers of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 4, 4-dimethyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 5-ethyl-1-hexene, 6-methyl-1-heptene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene.
- The curable composition according to Claim 4 wherein the polyolefin starting material is a polypropylene.
- The curable composition according to Claim 4 wherein the polyolefin starting material is a copolymer of propylene and ethylene wherein the concentration by weight of ethylene is less than 10%.
- The curable composition according to Claim 1 wherein the polycarboxylic compound is unsaturated polycarboxylic acids, anhydrides and esters thereof.
- The curable composition according to Claim 1 wherein the polycarboxylic compound is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, citraconic anhydride, aconitic anhydride, itaconic anhydride, dimethyl maleate, dimethyl fumarate, methyl ethyl maleate, dibutyl maleate, diptopyl maleate, and citric acid.
- The curable composition of Claim 8, wherein the ethylenically unsaturated polycarboxylic compound is maleic anhydride.
- The curable composition according to any one of the preceding Claims, wherein the composition is formaldehyde-free.
- A method for forming a substrate comprising: a) forming a curable aqueous composition comprising from 70 to 99%by dry weight based on total dry weight of the curable composition, an acrylic emulsion component, and from 1 to 30%by dry weight based on the total dry weight of the curable composition, a polyolefin emulsion component prepared by emulsifying a polycarboxylic-compound functionalized polyolefin starting material; b) contacting a flexible substrate with said curable aqueous composition; and c) heating said curable aqueous composition at a temperature of from 120℃. to 220℃.
- A treated substrate formed according to the method of Claim 11.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/482,989 US11286381B2 (en) | 2017-03-30 | 2017-03-30 | Formaldehyde-free curable composition |
RU2019133679A RU2732300C1 (en) | 2017-03-30 | 2017-03-30 | Curable composition without formaldehyde |
CN201780088165.0A CN110536944A (en) | 2017-03-30 | 2017-03-30 | Curable compositions without formaldehyde |
BR112019019306-5A BR112019019306B1 (en) | 2017-03-30 | 2017-03-30 | CURABLE COMPOSITION, METHOD FOR FORMING A SUBSTRATE AND TREATED SUBSTRATE |
PCT/CN2017/078707 WO2018176298A1 (en) | 2017-03-30 | 2017-03-30 | Formaldehyde-free curable composition |
MX2019011531A MX2019011531A (en) | 2017-03-30 | 2017-03-30 | Formaldehyde-free curable composition. |
EP17903450.9A EP3601463B1 (en) | 2017-03-30 | 2017-03-30 | Formaldehyde-free curable composition |
JP2019551345A JP2020515667A (en) | 2017-03-30 | 2017-03-30 | Formaldehyde-free curable composition |
TW107108961A TWI763799B (en) | 2017-03-30 | 2018-03-16 | Formaldehyde-free curable composition |
ARP180100667A AR111576A1 (en) | 2017-03-30 | 2018-03-21 | FREE FORMALDEHYDE CURABLE COMPOSITION |
JP2022003689A JP7357085B2 (en) | 2017-03-30 | 2022-01-13 | Formaldehyde-free curable composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2017/078707 WO2018176298A1 (en) | 2017-03-30 | 2017-03-30 | Formaldehyde-free curable composition |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018176298A1 true WO2018176298A1 (en) | 2018-10-04 |
Family
ID=63673915
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2017/078707 WO2018176298A1 (en) | 2017-03-30 | 2017-03-30 | Formaldehyde-free curable composition |
Country Status (10)
Country | Link |
---|---|
US (1) | US11286381B2 (en) |
EP (1) | EP3601463B1 (en) |
JP (2) | JP2020515667A (en) |
CN (1) | CN110536944A (en) |
AR (1) | AR111576A1 (en) |
BR (1) | BR112019019306B1 (en) |
MX (1) | MX2019011531A (en) |
RU (1) | RU2732300C1 (en) |
TW (1) | TWI763799B (en) |
WO (1) | WO2018176298A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114072479A (en) * | 2019-07-12 | 2022-02-18 | 陶氏环球技术有限责任公司 | Aqueous polymer formulations |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101225209A (en) * | 2006-12-22 | 2008-07-23 | 罗门哈斯公司 | Curable aqueous compositions |
WO2012068576A2 (en) * | 2010-11-19 | 2012-05-24 | Henkel Ag & Co. Kgaa | Adhesive compositions and use thereof |
CN102686692A (en) * | 2009-09-25 | 2012-09-19 | 汉高股份有限及两合公司 | Water-based adhesive for lamination of polymers to metal substrates |
CN104662080A (en) * | 2012-06-19 | 2015-05-27 | 陶氏环球技术有限责任公司 | Aqueous based blend composition and method of producing the same |
CN105008415A (en) * | 2013-02-15 | 2015-10-28 | H.B.富勒公司 | Reaction product of propylene polymer and wax, graft copolymers derived from polypropylene polymer and wax, hot melt adhesive compositions including the same, and methods of using and making the same |
CN105060736A (en) * | 2015-07-30 | 2015-11-18 | 南京京锦元科技实业有限公司 | Water soluble maleic anhydride modified PP emulsion for fiber surface treatment and application thereof |
CN105131874A (en) * | 2015-07-30 | 2015-12-09 | 南京京锦元科技实业有限公司 | Preparation method of water-soluble maleic anhydride modified PP emulsion |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4325856A (en) | 1980-01-02 | 1982-04-20 | The Dow Chemical Company | Sequential emulsion polymerization process |
DE3443964A1 (en) | 1984-12-01 | 1986-06-12 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING POLYMER DISPERSIONS THAT MAKE BLOCK-RESISTANT FILMS |
US4814373A (en) | 1984-12-20 | 1989-03-21 | Rohm And Haas Company | Modified latex polymer composition |
US6362280B1 (en) * | 1998-04-27 | 2002-03-26 | Honeywell International Inc. | Emulsible polyolefin wax |
WO2003091330A1 (en) * | 2002-04-26 | 2003-11-06 | Mitsubishi Chemical Corporation | Aqueous polypropylene dispersion, aqueous polypropylene composite emulsion composition, and use thereof |
JP4000977B2 (en) * | 2002-09-27 | 2007-10-31 | 三菱化学株式会社 | Polypropylene-based composite aqueous emulsion composition |
PT1587889E (en) * | 2003-01-30 | 2007-05-31 | Akzo Nobel Coatings Int Bv | Ambient temperature curing coating composition |
JP2005343920A (en) * | 2004-05-31 | 2005-12-15 | Mitsui Chemicals Inc | Water-based composition and polishing agent composition for floor |
JP2007169397A (en) * | 2005-12-20 | 2007-07-05 | Nippon Bee Chemical Co Ltd | Water-based one-pack type coating composition and coated article |
JP4598683B2 (en) * | 2006-01-25 | 2010-12-15 | 三井化学株式会社 | Laminated body |
US8173744B2 (en) | 2006-02-16 | 2012-05-08 | Kansai Paint Co., Ltd. | Water-based primer composition and coating method of plastic shaped articles using the composition |
JP4950696B2 (en) * | 2007-02-20 | 2012-06-13 | 関西ペイント株式会社 | Aqueous primer composition and coating method using the composition |
JP2010248393A (en) * | 2009-04-16 | 2010-11-04 | Kansai Paint Co Ltd | Water paint composition, and painting method using the same composition |
JP5378937B2 (en) * | 2009-09-30 | 2013-12-25 | 大日本塗料株式会社 | Conductive water-based primer composition and primer coating film |
GB2495227A (en) * | 2010-03-26 | 2013-04-03 | Umg Abs Ltd | Acid modified propylene aqueous dispersion, water-based coating composition using same and method for producing these |
CN107207891B (en) * | 2015-01-29 | 2020-09-04 | 关西涂料株式会社 | Aqueous coating composition |
JP6545552B2 (en) * | 2015-07-15 | 2019-07-17 | 東邦化学工業株式会社 | Aqueous dispersion |
-
2017
- 2017-03-30 WO PCT/CN2017/078707 patent/WO2018176298A1/en unknown
- 2017-03-30 RU RU2019133679A patent/RU2732300C1/en active
- 2017-03-30 US US16/482,989 patent/US11286381B2/en active Active
- 2017-03-30 EP EP17903450.9A patent/EP3601463B1/en active Active
- 2017-03-30 JP JP2019551345A patent/JP2020515667A/en active Pending
- 2017-03-30 MX MX2019011531A patent/MX2019011531A/en unknown
- 2017-03-30 CN CN201780088165.0A patent/CN110536944A/en active Pending
- 2017-03-30 BR BR112019019306-5A patent/BR112019019306B1/en active IP Right Grant
-
2018
- 2018-03-16 TW TW107108961A patent/TWI763799B/en active
- 2018-03-21 AR ARP180100667A patent/AR111576A1/en active IP Right Grant
-
2022
- 2022-01-13 JP JP2022003689A patent/JP7357085B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101225209A (en) * | 2006-12-22 | 2008-07-23 | 罗门哈斯公司 | Curable aqueous compositions |
CN102686692A (en) * | 2009-09-25 | 2012-09-19 | 汉高股份有限及两合公司 | Water-based adhesive for lamination of polymers to metal substrates |
WO2012068576A2 (en) * | 2010-11-19 | 2012-05-24 | Henkel Ag & Co. Kgaa | Adhesive compositions and use thereof |
CN104662080A (en) * | 2012-06-19 | 2015-05-27 | 陶氏环球技术有限责任公司 | Aqueous based blend composition and method of producing the same |
CN105008415A (en) * | 2013-02-15 | 2015-10-28 | H.B.富勒公司 | Reaction product of propylene polymer and wax, graft copolymers derived from polypropylene polymer and wax, hot melt adhesive compositions including the same, and methods of using and making the same |
CN105060736A (en) * | 2015-07-30 | 2015-11-18 | 南京京锦元科技实业有限公司 | Water soluble maleic anhydride modified PP emulsion for fiber surface treatment and application thereof |
CN105131874A (en) * | 2015-07-30 | 2015-12-09 | 南京京锦元科技实业有限公司 | Preparation method of water-soluble maleic anhydride modified PP emulsion |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114072479A (en) * | 2019-07-12 | 2022-02-18 | 陶氏环球技术有限责任公司 | Aqueous polymer formulations |
EP3997186A4 (en) * | 2019-07-12 | 2023-03-29 | Dow Global Technologies LLC | Aqueous polymer formulation |
CN114072479B (en) * | 2019-07-12 | 2024-01-05 | 陶氏环球技术有限责任公司 | Aqueous polymer formulations |
Also Published As
Publication number | Publication date |
---|---|
RU2732300C1 (en) | 2020-09-15 |
EP3601463B1 (en) | 2022-10-12 |
EP3601463A4 (en) | 2020-11-18 |
AR111576A1 (en) | 2019-07-31 |
US11286381B2 (en) | 2022-03-29 |
BR112019019306B1 (en) | 2022-09-06 |
JP7357085B2 (en) | 2023-10-05 |
TWI763799B (en) | 2022-05-11 |
TW201837105A (en) | 2018-10-16 |
JP2022062050A (en) | 2022-04-19 |
CN110536944A (en) | 2019-12-03 |
EP3601463A1 (en) | 2020-02-05 |
MX2019011531A (en) | 2019-12-09 |
BR112019019306A2 (en) | 2020-05-05 |
JP2020515667A (en) | 2020-05-28 |
US20210277217A1 (en) | 2021-09-09 |
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